Powdery White Vulcanization Promoter Composition and Rubber Compositions

ABSTRACT

A powdery white vulcanization promoter composition which is excellent in storage stability, the resistance of blends thereof with rubbers or the like to heat build-up, and design; and rubber compositions containing the same. Specifically, a vulcanization promoter composition which comprises a modified calcium carbonate (A) surface-treated with a fatty acid or a resin acid and a silicic acid, an inorganic filler (B) exhibiting an oil absorption of as high as 50 to 300 ml/100 g, and a vulcanization promoter component (C) liquid at ordinary temperatures, characterized in that the (A):(B) mixing ratio is within the range of 30:70 to 95:5 and the content of (C) is 30 to 80 wt % based on the whole of the promoter composition.

TECHNICAL FIELD

The present invention relates to a powdery white vulcanization promotercomposition, and a rubber composition containing the same.

BACKGROUND ART

conventionally, precipitated silica has mainly been used as a whitereinforcing filler in rubber compositions. However, a rubber compositioninto which precipitated silica is blended has problems as described inthe following, as compared with other white fillers: (1) the viscosityof the rubber which has not been vulcanized is high; (2) the vulcanizingspeed becomes small; (3) the precipitated silica is not easily dispersedsince the silica has a high self-aggregating property; and (4) therubber elasticity is damaged although the reinforcing performancebecomes high.

As a means for solving such problems, attempts of incorporating variousvulcanization promoters, such as a silane coupling agent, are made(Patent Documents 1 and 2).

Usually, a silane coupling agent is in a liquid form at ordinarytemperature. However, the agent is not easily mixed with rubber which isthe partner material therewith since the rubber is in a solid form.Moreover, the agent is not uniformly dispersed with ease since theamount thereof added to the rubber is relatively small.

Known is a rubber composition wherein a silane coupling agent issupported on carbon black at an amount of about 50%, thereby improvingthe workability and reinforcing performance, in order to make thehandling easy and improve the dispersibility (Patent Document 3).However, the composition is unsuitable for colored rubber products sincethe rubber is colored into black.

It can be supposed that a silane coupling agent is supported on a whitefiller such as calcium carbonate (Patent Document 4), or precipitatedsilica or hydrated calcium silicate (Patent Document 5) in order toimprove the designability. However, since the water content inprecipitated silica is high, it is feared that the silane coupling agentis inactivated. Thus, there arise problems regarding the storagestability and the storage control. Conventional calcium carbonate cannotbe made into a high concentration since the calcium carbonate exhibits asmall oil absorption. Moreover, the calcium carbonate has a problemregarding the reinforcing performance since particles of the calciumcarbonate are not smaller than those of carbon black or precipitatedsilica.

Patent Document 1: Japanese Patent Application Laid Open (JP-A) No.2003-155380

Patent Document 2: JP-A No. 2003-192842

Patent Document 3: JP-A No. 54-68860

Patent Document 4: JP-A No. 56-104950

Patent Document 5: JP-A No. 51-23540

DISCLOSURE OF THE INVENTION

An object of the present invention is to provide a powdery whitevulcanization promoter composition which is excellent in storagestability, resistance to heat build-up when the composition is blendedinto rubber or the like, and designability; and a rubber compositioncontaining the composition.

The powdery white vulcanization promoter composition of the presentinvention is a powdery white vulcanization promoter compositioncomprising modified calcium carbonate (A) surface-treated with a fattyacid or a resin acid and a silisic acid, a highly oil-absorbinginorganic filler (B) exhibiting an oil absorption of 50 to 300 mL/100 g,and a vulcanization promoter (C) which is in a liquid form at ordinarytemperature (room temperature), wherein the mixing ratio by weight ofthe modified carbon calcium (A) to the inorganic filter (B) (the ratioof (A):(B)) is within a range of from 30:70 to 95:5, and the content bypercentage of the vulcanization promoter (C) is from 30 to 80% by weightbased on the total of the composition.

The primary particle diameter of the modified calcium carbonate (A) ispreferably from 0.01 to 0.5 μm.

As the vulcanization promoter (C), for example, at least one selectedfrom an organic silane compound, an organic titanate compound, and anorganic aluminate compound can be used.

As the inorganic filler (B), for example, at least one selected fromsilica, aluminum hydroxide, calcium silicate, and magnesium carbonatecan be used.

The rubber composition of the present invention is characterized in thatthe above-mentioned powdery white vulcanization promoter composition ofthe present invention and precipitated silica are blended into a rubber.

It is preferable that the powdery white vulcanization promotercomposition is contained in the rubber composition of the presentinvention so as to set the amount of the vulcanization promoter (C) tothe range of 1 to 40 parts by weight based on 100 parts by weight of theprecipitated silica.

The powdery white vulcanization promoter composition of the presentinvention is a powdery material containing the liquid vulcanizationpromoter for vulcanizing rubber or the like; therefore, the compositionis easily handled, and the vulcanization promoter can be uniformlydispersed when the composition is blended into rubber or the like.Moreover, the composition can be colored since the composition is white.Thus, the composition can be used to produce a colored rubber product.Accordingly, a rubber product excellent in designability can beproduced.

Moreover, the powdery white vulcanization promoter composition of thepresent invention is excellent in storage stability. For this reason,the composition can be stored for a long term, and the handling andstorage control thereof are easy.

When the powdery white vulcanization promoter composition of the presentinvention is blended into rubber or the like, good resistance to heatbuild-up can be given thereto.

Since the rubber composition of the present invention contains thepowdery white vulcanization promoter composition of the presentinvention, the rubber composition is excellent in resistance to heatbuild-up and designability.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention will be specifically described hereinafter.

<Modified Calcium Carbonate (A)>

The modified calcium carbonate used in the present invention issurface-treated with a fatty acid or a resin acid and a silisic acid.

It is sufficient that the modified calcium carbonate has a structurewherein the whole or a part of the surface of raw material calciumcarbonate particles or treated calcium carbonate particles is coveredwith a fatty acid, a resin acid and a silisic acid. Thus, it is notnecessarily essential that the whole of the surface is continuouslycovered. In addition, the order of the treatments is not limited.

As calcium carbonate, which is the starting material of the modifiedcalcium carbonate, known ground calcium carbonate or synthetic(precipitating) calcium carbonate, or the like may be used.

Ground calcium carbonate can be prepared by a method of pulverizingnaturally-produced calcium carbonate ore in a dry or wet manner, or someother method, using a roller mill, a high-speed rotary mill (impactshearing mill), a container-driving medium mill (ball mill), a mediumstirring mill, a planetary mill, a jet mill or the like.

Synthetic (precipitating) calcium carbonate can be prepared by a limemilk-carbon dioxide gas reaction method, a calcium chloride-sodium ashreaction method, a lime milk-sodium ash reaction method, or any otherknown method. Specifically, an example of the lime milk-carbon dioxidereaction method is a method comprising the steps of: performingmixed-firing of limestone ore with corks, a petroleum fuel (heavy oil orlight oil), natural gas, LPG or the like to produce caustic lime;hydrating this caustic lime to prepare a calcium hydroxide slurry; andthen bubbling carbon dioxide generated in the mixed-firing into thisslurry to react with each other; and thereby producing calciumcarbonate. By setting conditions in the carbon dioxide gas reaction,fine particles in desired submicron order can be obtained.

When the modified calcium carbonate in the present invention is observedwith a scanning electron microscope, the particle shape of primaryparticles, which are respectively a minimum unit, is cubic or spherical.The primary particle diameter of the modified calcium carbonate in thepresent invention can be measured with a scanning electron microscope,as described above, and is preferably from about 0.01 to 0.5 μm, morepreferably from 0.01 to 0.1 μm.

When the particle shape is cubic, the primary particle diameter of themodified calcium carbonate in the present invention represents thelength of each of the sides. When the shape is spherical, the primaryparticle diameter represents the diameter. The modified calciumcarbonate in the present invention may form a secondary particle whereinthe primary particles aggregate.

If the particles are too large, the vulcanization promoter cannot besufficiently retained and further reinforcing performances such asmodulus and abrasion resistance may be unfavorably damaged. On the otherhand, if the particles are too small, the dispersibility deteriorates sothat the reinforcing effect onto a rubber component may be unfavorablydamaged.

Examples of the fatty acids used in the modified calcium carbonate inthe present invention include saturated or unsaturated fatty acidshaving 6 to 24 carbon atoms, and salts or esters thereof.

Examples of the saturated or unsaturated fatty acids having 6 to 24carbon atoms include stearic acid, palmitic acid, lauric acid, behenicacid, oleic acid, erucic acid, and linoleic acid. Particularly, stearicacid, palmitic acid, lauric acid, and oleic acid are preferred. Thesemay be used in the form of a mixture of two or more thereof.

Examples of the fatty acid salts include alkali metal salts and alkalineearth metal salts.

Examples of the fatty acid esters include esters each made fromsaturated or unsaturated fatty acids having about 6 to 24 carbon atomsand a lower alcohol having about 6 to 18 carbon atoms.

Examples of the method for the treatment with the fatty acids aremethods as described below.

First, the fatty acid is heated in an aqueous solution of an alkalimetal, such as an aqueous solution of NaOH or an aqueous solution ofKOH, to saponify the fatty acid (converting the acid into a metal saltsuch as a Na salt or a K salt), thereby turning the acid into a solutionform. Next, an aqueous suspension of calcium carbonate is beforehandheated to 30 to 50° C., and to this suspension is added thesolution-form fatty acid soap. The resultant is stirred to mix thecomponents to form a layer treated with the fatty acid. In the case ofusing a soap such as fatty acid Na as it is, a heated aqueous solutionthereof is beforehand prepared, and treatment is conducted in the sameway as described above.

The treatment can be conducted by use of the fatty aid withoutsaponifying the acid. For example, calcium carbonate is stirred whileheated to the melting point of the fatty acid or higher. Thereto isadded the fatty acid, and the resultant is stirred to mix thecomponents, whereby a layer treated with the fatty acid can be formed.

Examples of the resin acid used in the present invention include abieticacids, such as abietic acid, dehydroabietic acid and dihydroabieticacid, and polymers thereof, disproportionated rosin, hydrogenated rosin,polymerized rosin, and salts thereof (such as alkali metal salts andalkaline earth metal salts thereof) or esters thereof. Among these,abietic acid and dehydroabietic acid are preferred.

As the method for treatment with a resin acid, the same method with afatty acid can be adopted. Specifically, first, the resin acid is heatedin an aqueous solution of an alkali metal, such as an aqueous solutionof NaOH or an aqueous solution of KOH, to saponify the resin acid(converting the acid into a metal salt such as a Na salt or a K salt),thereby turning the acid into a solution form. Next, an aqueoussuspension of calcium carbonate is beforehand heated to 30 to 50° C.,and this suspension is added to the solution-form resin acid soap. Theresultant is stirred to mix the components to form a layer treated withthe resin acid. In the case of using a soap such as resin acid Na as itis, a heated aqueous solution thereof is beforehand prepared, andtreatment is conducted in the same way as described above. The treatmentcan be conducted by use of the resin aid without saponifying the acid.For example, calcium carbonate is stirred while heated to the meltingpoint of the resin acid or higher. Thereto is added the resin acid, andthe resultant is stirred to mix the components, whereby a layer treatedwith the resin acid can be formed.

The adhesion amount of at least one organic acid selected from the groupconsisting of fatty acids and the resin acids is not particularlylimited, and the amount is usually from about 0.5 to 20 parts by weightbased on 100 parts by weight of calcium carbonate as a raw material. Theamount is more preferably from about 1 to 15 parts by weight, even morepreferably from about 2 to 12 parts by weight therefor.

In the present invention, the silicic acid used in the modified calciumcarbonate can be produced by a known method. For example, silicahydrosol produced by an acid discomposing method, or amorphous silicahydrosol produced by adding, to a sodium silicate solution, an inorganicacid such as hydrochloric acid or sulfuric acid, aluminum sulfate, anorganic acid such as acetic acid or acrylic acid, or any other acidicmaterial such as carbon dioxide, can be used. Alternatively, silicahydrosol produced by a dialysis method of passing sodium silicatethrough a semipermeable membrane, or silica hydrosol produced by an ionexchange method of using an ion exchange resin can be used.

An example of the method for treating calcium carbonate with the silicicacid is a method of adding sodium silicate having an appropriateconcentration to a calcium carbonate slurry, dropping an acidic materialsuch as an inorganic acid or an organic acid thereto while stirring theslurry, and then treating the surface of calcium carbonate with theproduced silica hydrosol.

In the case of using silica hydrosol prepared in advance, the treatmentcan be conducted by adding the silica hydrosol to a calcium carbonateslurry and then stirring the slurry vigorously.

The adhesion amount of the silica hydrosol used in the present inventionto calcium carbonate is not particularly limited, and the amount isusually from about 0.5 to 15 parts by weight based on 100 parts byweight of calcium carbonate as a raw material, more preferably fromabout 1 to 12 parts by weight, even more preferably from about 2 to 10parts by weight therefor. The adhesion amount can be appropriatelyadjusted in accordance with the BET specific surface area of calciumcarbonate, which is an adhesion object, and other factors.

If the adhesion amount of silica hydrosol to calcium carbonate is toosmall, the number of reaction sites to which a vulcanization promotersuch as a silane coupling agent is to be bonded is small so that desiredrubber property may not be expressed. On the other hand, if the adhesionamount is too large, silica hydrosol is excessively present, besidessilica hydrosol adhering to the calcium carbonate surface, in thesolution. Thus, silica hydrosol causes calcium carbonate to be intenselyaggregated and solidified when the sol is dried. As a result, coarseparticles which are not easily pulverized increase. It is feared thatthe calcium carbonate filler containing such coarse particles causes afall in the tear strength, the flex cracking resistance and otherproperties of the polymer.

In the present invention, the order of the surface treatment with afatty acid or a resin acid and the treatment with a silisic acid are notparticularly limited as described above. It is preferred to subject raw(i.e., non-treated) calcium carbonate firstly to surface treatment withthe silicic acid, and then subject the resultant to surface treatmentwith a fatty acid or a resin acid.

The average particle diameter of the modified calcium carbonate used inthe present invention can be set at will as long as desired advantageouseffects are produced. The average particle diameter is preferably from0.01 to 0.5 μm, more preferably from 0.01 to 0.3 μm, even morepreferably from 0.01 to 0.1 μm. This average particle diameter can bemeasured by observing the particles with, for example, a scanningelectron microscope.

If the particle diameter is too large, a rubber composition having asufficient abrasion resistance cannot be unfavorably obtained. On theother hand, if the particle diameter is too small, the dispersibilitydeteriorates so that the reinforcing effect onto the rubber componentmay be unfavorably damaged.

The BET specific surface area of the modified calcium carbonate ispreferably from about 5 to 120 m²/g, more preferably from about 10 to120 m²/g, even more preferably from about 60 to 110 m²/g.

If the BET specific surface area is less than 5 m²/g, a sufficientabrasion resistance cannot be unfavorably obtained. If the area is morethan 120 m²/g, the scatterability unfavorably becomes strong.

<Inorganic Filler (B)>

Examples of the highly oil-absorbing inorganic filler used in thepresent invention include silica, aluminum hydroxide, calcium silicate,magnesium carbonate, and superfine zinc particles. These may be usedalone or in the form of a mixture of two or more thereof.

As silica, for example, silica which is ordinarily used for rubberreinforcement can be used. Specific examples thereof includeprecipitated silica and fumed silica.

In the case of, for example, silica, it is more preferred to use silicathe BET specific surface area of which is 80 m²/g or more, morepreferably from 80 to 400 m²/g, even more preferably from 80 to 250m²/g, the specific surface area being based on a nitrogen adsorptionmethod.

Silica having a BET specific surface area in the above-mentioned rangeis particularly preferred since the silica has a good dispersibility,exhibits a large absorbing amount of the vulcanization promoter, and isexcellent in reinforcing performances such as tensile property, tearstrength, and abrasion resistance.

The oil absorption is preferably from 50 to 600 mL/100 g, morepreferably from 70 to 300 mL/100 g, even more preferably from 100 to 300mL/100 g. The filler having an oil absorption in the above-mentionedrange exhibits a large retention amount of the vulcanization promoter soas to maintain powder natures easily.

<Vulcanization Promoter (C)>

The vulcanization promoter (C) used in the present invention is notparticularly limited as long as the promoter (C) is a component capableof activating vulcanization in rubber or the like. Examples thereofinclude an organic silane compound, an organic titanate compound, and anorganic aluminate compound. Besides these, a known vulcanizationpromoter or vulcanization promotion auxiliary, or the like is used.These may be used alone or in the form of a mixture of two or morethereof.

As the organic silane, for example, a material known as a silanecoupling agent can be used. Examples of the silane coupling agentinclude vinyltrichlorosilane, vinyltrimethoxysilane,vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, β-(3,4epoxycyclohexyl)ethyltrimethoxysilane,γ-(2-aminoethyl)aminopropyltrimethoxysilane,γ-glycidoxypropyltrimethoxysilane,γ-glycidoxypropyltrimethyldiethoxysilane,γ-glycidoxypropyltriethoxysilane,γ-methacryloxypropylmethyldimethoxysilane,γ-methacryloxypropyltrimethoxysilane,γ-methacryloxypropylmethyldiethoxysilane,γ-methacryloxypropyltriethoxysilane,N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane,N-β(aminoethyl)γ-aminopropyltrimethoxysilane,N-β(aminoethyl)γ-aminopropyltriethoxylsilane,γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane,N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane,γ-mercaptopropyltrimethoxysilane,bis-(3-[triethoxysilyl]-propyl)-disulfone, andbis-(3-[triethoxysilyl]-propyl)-tetrasulfone (TESPT). These may be usedalone or in combination of two or more thereof.

It is preferred to use, among these,γ-(2-aminoethyl)aminopropyltrimethoxysilane,N-β(aminoethyl)γ-aminopropyltrimethoxysilane,γ-mercaptopropyltrimethoxysilane, orbis-(3-[triethoxysilyl]-propyl)-tetrasulfone.

As the organic titanate compound, any titanate coupling agent that isblended into conventional rubbers or plastics can be blended. Examplesthereof include isopropyltriisostearoyl titanate,isopropyltridodecylbenzenesulfonyl titanate,isopropyltris(dioctylpyrophosphate) titanate,tetraisopropylbis(dioctylphosphate) titanate,tetraoctylbis(ditridecylphosphate) titanate,tetra(2,2-diallyloxymethyl-1-butyl)bis(di-tridecyl)phosphate titanate,bis(dioctylpyrophosphate)oxyacetate titanate,bis(dioctylpyrophophate)ethylene titanate, isopropyltrioctanoyltitanate, isoproypldimethacrylisostearoyl titanate,isopropylisostearoyldiacryl titanate, isopropyltri(dioctylphosphate)titanate, isopropyltricumylphenyl titanate,isopropyltri(N-amidoethyl.aminoethyl) titanate, dicumylphenyloxyacetatetitanate, and diisostearoylethylene titanate. These may be used alone orin combination of two or more thereof. Among these,isopropyltriisostearoyl titanate is preferred.

As the organic aluminate compound, an aluminate coupling agent can beused. An example thereof is acetoalkoxyaluminum diisopropylate.

<Preparation of the Powdery White Vulcanization Promoter Composition>

The powdery white vulcanization promoter composition of the presentinvention can be prepared by mixing the modified calcium carbonate (A),the inorganic filler (B), and the vulcanization promoter (C). The methodfor the mixing is not particularly limited. In general, the followingmethod is preferably adopted: a method of mixing the modified calciumcarbonate (A) and the inorganic filler (B) that are powdery with eachother at a predetermined ratio, adding the vulcanization promoter (C)which is in a liquid form while stirring the powdery mixture, and thenmixing the components.

The mixing ratio of the modified calcium carbonate (A) to the inorganicfiller (B) (the ratio of (A):(B)) is within a range of from 30:70 to95:5. The ratio more preferably is within a range of from 30:70 to90:10. If the mixing ratio of the inorganic filler (B) is too small, thevulcanization promoter (C) bleeds easily with the passage of time. Thus,the state of the powder may not be kept with ease. If the ratio of theinorganic filler (B) is too large, the amount of the modified calciumcarbonate (A) decreases relatively so that the vulcanization promoter(C) may be inactivated. Thus, the storage stability may decline.

The content by percentage of the vulcanization promoter (C) is from 30to 80% by weight based on the total (the whole of the modified calciumcarbonate (A), the inorganic filler (B), and the vulcanization promoter(C)), preferably from 30 to 70% by weight thereof, more preferably from40 to 70% by weight thereof.

If the content by percentage of the vulcanization promoter (C) is lessthan 30% by weight, a large amount of the vulcanization promotercomposition needs to be blended into rubber or others. Thus, theworkability of the rubber or others or the mechanical strength thereofmay lower. If the content by percentage of the vulcanization promoter(C) is too large, the nature or state of the powder may not be kept.

The rubber composition of the present invention will be specificallydescribed hereinafter.

<Rubber Component>

As the rubber component, at least one selected from natural rubber anddiene synthetic rubbers is used.

The diene synthetic rubbers which can be used may each be a diene rubberwhich can be crosslinked. Specific examples of the diene syntheticrubbers include cis-1,4-polyisoprene, emulsion-polymerized styrenebutadiene copolymer, solution-polymerized styrene butadiene copolymer,low cis-1,4-polybutadiene, high cis-1,4-polybutadiene,ethylene-propylene-diene copolymer, chloroprene, halogenated butylrubber, and acrylonitrile-butadiene rubber.

Among the above-mentioned rubber components, there can be preferablyused natural rubber, cis-1,4-polyisoprene, emulsion-polymerized styrenebutadiene copolymer, solution-polymerized styrene butadiene copolymer,low cis-1,4-polybutadiene, or high cis-1,4-polybutadiene.

Regarding the rubber component, any one of the above-mentioned naturalrubber or the diene synthetic rubbers may be used, or a mixture of twoor more thereof may be used. The mixing ratio therebetween can beappropriately set in accordance with required properties, and others.

<Rubber Composition>

The rubber composition of the present invention is a composition whereinprecipitated silica and the vulcanization promoter composition of thepresent invention are blended into the rubber component.

The precipitated silica used in the present invention may beprecipitated silica which is ordinarily blended as a reinforcing agentinto rubber. Usually, the blended amount of the precipitated silica ispreferably from about 10 to 100 parts by weight based on 100 parts byweight of the rubber component, more preferably from 20 to 100 parts byweight therefor, in particular preferably from 20 to 90 parts by weighttherefor.

If the blended amount of the precipitated silica is too small, theabrasion resistance of the rubber composition unfavorably lowers. If theamount is too large, the viscosity of the rubber rises so that theworkability unfavorably deteriorates.

Regarding the blended amount of the vulcanization promoter composition,the composition is blended in such a manner that the amount of thevulcanization promoter (C) in the vulcanization promoter composition isset preferably into 1 to 40 parts by weight, more preferably into 5 to20 parts by weight, in particular preferably into 5 to 10 parts byweight based on the 100 parts by weight of the precipitated silica. Thereason why the blended amount of the vulcanization promoter compositionis decided on the basis of the blended amount of the precipitated silicais that the blended amount of the vulcanization promoter (C) isgenerally decided on the basis of the blended amount of precipitatedsilica.

If the blended amount of the vulcanization promoter composition is toosmall, the reinforcing performance cannot be unfavorably improved whenthe composition is blended into the rubber. If the amount is too large,costs for the rubber composition unfavorably increase.

If necessary, a known compounding agent may be added to the rubbercomposition of the present invention. For example, the other fillerincluding fumed silica, clay, talc, aluminum hydroxide, and carbon blackcan be appropriately used together. Furthermore, if desired, a processoil, an antioxidant, an age resistor, an activator, an additive such asstearic acid, zinc oxide or wax, or a vulcanizing agent such as sulfuror a vulcanization promoter can be blended.

The rubber composition of the present invention can be produced bykneading the rubber component, the precipitated silica, thevulcanization promoter composition, and optionally-selected compoundingagents, heating the mixture, extruding the mixture, and subjecting theresultant to vulcanization and others.

Conditions for the kneading are not particularly limited, and can beappropriately selected from the charging volume to a kneading machine,the rotary speed of the rotor, the ram pressure, the kneadingtemperature, the kneading time, the kind of the kneading machine, andthe like in accordance with the purpose. The kneading machine is notparticularly limited, and both of a closed type or of an open type maybe used. Examples thereof are a known machine ordinarily used to knead arubber composition. Specific examples thereof include a Banbury mixer(registered trade name), an Intermix (registered trademark), a kneader,and roll.

Conditions for the heating are not particularly limited, and can beappropriately selected about the heating temperature, the heating time,and the heating machine, and the like in accordance with the purpose.The heating machine is, for example, a roll mill ordinarily used to heata rubber composition.

Conditions for the extrusion are not particularly limited, and can beappropriately selected from the extrusion time, the extrusion speed, theextruder, the extrusion temperature and the like in accordance with thepurpose. The extruder is, for example, an extruder ordinarily used toextrude a rubber composition. The extrusion temperature can beappropriately decided.

The machine, manner and conditions used in the vulcanization are notparticularly limited, and can be appropriately selected in accordancewith the purpose. The machine used in the vulcanization is, for example,a molding vulcanizing machine using a mold. In the conditions for thevulcanization, the vulcanization temperature is usually from 100 to 190°C.

EXAMPLES

The present invention will be more specifically described with respectto working examples and comparative examples hereinafter. However, thepresent invention is not limited to the working examples.

[Preparation of Modified Calcium Carbonate]

A synthetic calcium carbonate slurry having a BET specific surface areaof 75 m²/g was heated to 40° C. while stirred sufficiently. Sodiumsilicate (sodium silicate (manufactured by Wako Pure ChemicalIndustries, Ltd.)) was diluted water 10 times at room temperature, and 7parts by weight of the aqueous solution of sodium silicate were added to100 parts by weight of this synthetic calcium carbonate. Dilutedhydrochloric acid was introduced into the solution to produce a silicalayer on the surface of the calcium carbonate. Next, to 100 parts byweight of this synthetic calcium carbonate, 5 parts by weight of mixedfatty acids (oleic acid, stearic acid and palmitic acid (manufactured byWako Pure Chemical Industries, Ltd.)) were added, and were heated to 90°C. and stirred to be saponified. Next, the resultant was dehydrated,dried and pulverized to yield calcium carbonate powder having a fattyacid layer. The yielded calcium carbonate was referred to as modifiedcalcium carbonate a.

[Preparation of Powdery White Vulcanization Promoter Compositions]

Examples 1 to 5

The modified calcium carbonate a was used as the modified calciumcarbonate (A) and precipitated silica described below was used as thehighly oil-absorbing inorganic filler (B). A silane coupling agent(TESPT) described below was used as the vulcanization promoter (C). Eachblend ratio shown in Tables 1 and 3 was used to prepare each powderywhite vulcanization promoter composition.

Specifically, the modified calcium carbonate and the inorganic filler aspowdery components were stirred and mixed in a super mixer, and then thevulcanization promoter was sprayed onto this mixture while the mixturewas stirred. In this way, each powdery white vulcanization promotercomposition was prepared.

Precipitated silica: white carbon, oil absorption: 200 mL/100 g, tradename: “Nipsil VN3”, manufactured by Nippon Silica Industrial Co., Ltd.

Silane coupling agent: bis-(3-[triethoxysilyl]-propyl)tetrasulfone(TESPT), manufactured by Degussa Co.

Comparative Examples 1 to 5

The modified calcium carbonate a or comparative calcium carbonate b or cdescribed below was used as calcium carbonate, and, at each blend ratioshown in Tables 1 and 2, the calcium carbonate, the precipitated silicaand TESPT were stirred and mixed in the same way as described above toprepare each powdery white vulcanization promoter composition.

Comparative calcium carbonate b: synthetic calcium carbonate, tradename: “Silver W”, manufactured by Shiraishi Kogyo Kaisha, Ltd.

Comparative calcium carbonate c: calcium carbonate obtained in the sameway for producing the modified calcium carbonate a except that sodiumsilicate was not added was referred to as comparative calcium carbonatec.

[Preparation of Rubber Compositions]

Each of the above-mentioned vulcanization promoter compositions wasblended into a rubber component to prepare a rubber composition. As therubber component, SBR described below was used, and the following wereused as additives: zinc oxide, stearic acid, precipitated silica, aprocess oil, an age resistor, a vulcanization promoter D, avulcanization promoter CZ, and sulfur. As the process oil, the ageresistor and the vulcanization promoter, products described below werespecifically used. The used precipitated silica was the same as usedwhen the vulcanization promoter composition was prepared.

The vulcanization promoter composition was added to a rubber compositionin such a manner that the amount of TESPT in the vulcanization promotercomposition was 5 parts by weight based on 100 parts by weight of therubber (at an amount of 10 parts by weight based on 100 parts by weightof the precipitated silica). Accordingly, the vulcanization promotercomposition was added at an amount of 10 parts by weight (each of theexamples except Examples 4 and 5), at an amount of 16.7 parts by weight(Example 4), or at an amount of 7.1 parts by weight (Example 5) for 100parts by weight of the rubber.

(Composition of the Rubber Composition)

SBR: 100 parts by weight

Zinc oxide: 4 parts by weight

Stearic acid: 2 parts by weight

Precipitated silica: 50 parts by weight

Process oil: 25 parts by weight

Age resistor: 1 part by weight

Vulcanization promoter D: 1 part by weight

Vulcanization promoter CZ: 1 part by weight

Sulfur: 2 parts by weight

Vulcanization promoter composition: 10 parts by weight, 16.7 parts byweight, or 7.1 parts by weight

SBR: solution-polymerized SBR, trade name: “S-SBR SL552”, manufacturedby JSR Corp.; amount of bonded styrene: 24%; cis-1,4 bond amount: 20%

Process oil: trade name: “NP-24”, manufactured by Idemitsu Kosan Co.,Ltd.

Age resistor: trade name: “NOCRAC 224”, manufactured by OuchiShinkoChemical Industrial Co., Ltd.

Vulcanization promoter D: trade name “NOCCELER D”, manufactured byOuchiShinko Chemical Industrial Co., Ltd.

Vulcanization promoter CZ: trade name “NOCCELER CZ”, manufactured byOuchiShinko Chemical Industrial Co., Ltd.

The mix of each of the vulcanization promoter compositions wasperformed, using 8-inch two roll. The resultant rubber composition wassubjected to pressing vulcanization on the basis of an optimalvulcanization time tc(90) calculated out by means of a curelasto meter(at 160° C.), to yield a rubber sheet 2 mm in thickness.

Here, in the incorporation of each of the vulcanization promotercompositions of Examples 1 to 5 and Comparative Examples 1 to 5, thefollowing three vulcanization promoter composition species were used: aspecies of the vulcanization promoter composition immediately after thepreparation thereof; a species of the vulcanization promoter compositionstored in a paper bag for 3 months; and a species of the vulcanizationpromoter composition stored in the paper bag for 6 months. Accordingly,in each of the Examples and the Comparative Examples, three rubbercomposition species after a lapse of 0 month, that of 3 months, and thatof 6 months were prepared.

[Evaluation of the Rubber Compositions]

In the rubber sheet obtained from each of the rubber compositions ofExamples 1 to 5 and Comparative Examples 1 to 5, an unvulcanized rubbertest, a tensile test, and an abrasion test were made by methodsdescribed below.

1. Tensile Test

A Schopper tensile strength tester was used to measure the 300% modulus(the tensile strength at the time of 300% stretch) at 23° C. inaccordance with a method prescribed in JIS K 6251.

2. Heat Build-Up

A flexometer was used to measure the heat build-up temperature from aninitial temperature of 40° C. in accordance with a method prescribed inJIS K 6265. The used test piece was a columnar piece having a diameterof 17.80 mm and a height of 25.0 mm, and a static compressive stress of1 MPa was applied thereto 1800 times per minute at a stroke of 4 m/m.When 25 minutes elapsed, the heat build-up temperature (Δt) wasmeasured.

The evaluation results are shown in Tables 1 to 3. TABLE 1 Comp. Ex. 1Ex. 1 Ex. 2 Ex. 3 Comp. Ex. 2 Vulcanization Modified 49 45 35 20 10Promoter Calcium Composition Carbonate a Precipitated  1  5 15 30 40Silica TESPT 50 50 50 50 50 Form Pasty Powdery Powdery Powdery PowderyRubber Elapsed Time 0 3 6 0 3 6 0 3 6 0 3 6 0 3 6 Composition (months)300% Modulus — — — 8.5 8.3 8.7 8.5 8.3 8.5 8.5 8.4 8.7 8.8 8.7 8.3 (MPa)Heat build-up — — — 11 10 8 12 10 12 12 12 12 20 40 <50 (° C.)

TABLE 2 Comp. Ex. 3 Comp. Ex. 4 Comp. Ex. 5 Vulcanization Comparative —— 35 Promoter Calcium Composition Carbonate b Comparative — 35 — CalciumCarbonate c Precipitated 50 15 15 Silica TESPT 50 50 50 Form PowderyPowdery Pasty Rubber Elapsed Time 0 3 6 0 3 6 0 3 6 Composition (months)300% Modulus 8.3 8.9 4.5 8.3 8.5 8.9 — — — (MPa) Heat build-up 25 40 50>11 15 21 — — — (° C.)

As is evident form Tables 1 and 2, the rubber compositions wherein thevulcanization promoter compositions of Examples 1 to 3 according to thepresent invention were used exhibited stable rubber properties evenafter the three and six months elapsed. On the other hand, it isunderstood that in Comparative Example 3, wherein only precipitatedsilica was used as a powdery component, the heat build-up at the time ofthe dynamic fatigue was large from immediately after the start of thetest, and the 300% modulus declined after the lapse of the 6 months. Itappears that this was based on a deterioration in the activity of thevulcanization promoter, resulting from a change in the component withthe passage of time.

It can be understood that in Comparative Example 4, wherein thecomparative calcium carbonate c treated with no silica was used, theheat build-up deteriorated in comparison with that in Example 2according to the present invention.

In Comparative Examples 1 and 5, the form of the vulcanization promotercomposition was pasty, so as not to be powdery. Accordingly, inComparative Examples 1 and 5, evaluation of the rubber composition wasnot made.

As is clear from comparison of Examples 1 to 3 with Comparative Examples1 to 5, the use of the vulcanization promoter composition of the presentinvention gives a small heat build-up when dynamic fatigue is given tothe rubber composition, and gives a small change in the modulus with anelapsed time. In other words, it is understood that a good storagestability and a good resistance to heat build-up can be obtained. It isalso understood that the incorporation of the modified calcium carbonateat a blend ratio in the present invention gives a good storage stabilityand a good resistance to heat build-up. TABLE 3 Ex. 4 Ex. 3 Ex. 5Vulcanization Modified 28 20 12 Promoter Calcium Composition Carbonate aPrecipitated 42 30 18 Silica TESPT 30 50 70 Form Powdery Powdery PowderyRubber Elapsed Time 0 3 6 0 3 6 0 3 6 Composition (months) 300% Modulus8.4 8.5 8.3 8.5 8.4 8.7 8.6 8.9 8.8 (MPa) Heat build-up 12 11 13 12 1212 13 12 13 (° C.)

As is clear form the results shown in Table 3, when TESPT, which is avulcanization promoter, is used at a blend ratio in the range in thepresent invention, a good storage stability and a good heat build-upresistance can be obtained.

1. A powdery white vulcanization promoter composition comprising; amodified calcium carbonate (A) surface-treated with a fatty acid or aresin acid and a silisic acid; a highly oil-absorbing inorganic filler(B) exhibiting an oil absorption of 50 to 300 mL/100 g; and avulcanization promoter (C) which is in a liquid form at ordinarytemperature; wherein the mixing ratio by weight of the modified carboncalcium (A) to the inorganic filter (B) (the ratio of (A):(B)) is withina range of from 30:70 to 95:5, and the content by percentage of thevulcanization promoter (C) is from 30 to 80% by weight based on thetotal of the composition.
 2. The powdery white vulcanization promotercomposition according to claim 1, wherein the modified calcium carbonate(A) has an average primary particle diameter of 0.01 to 0.5 μm.
 3. Thepowdery white vulcanization promoter composition according to claim 1,wherein the vulcanization promoter (C) is at least one from an organicsilane compound, an organic titanate compound, and an organic aluminatecompound.
 4. The powdery white vulcanization promoter compositionaccording to claim 1, wherein the inorganic filler (B) is at least oneselected from silica, calcium silicate, magnesium carbonate, andaluminum hydroxide.
 5. A rubber composition, wherein the powdery whitevulcanization promoter composition according to claim 1, andprecipitated silica are blended into a rubber.
 6. The rubber compositionaccording to claim 5, wherein the powdery white vulcanization promotercomposition is contained so as to set the amount of the vulcanizationpromoter (C) into the range of 1 to 40 parts by weight based on 100parts by weight of the precipitated silica.
 7. The powdery whitevulcanization promoter composition according to claim 2, wherein thevulcanization promoter (C) is at least one from an organic silanecompound, an organic titanate compound, and an organic aluminatecompound.
 8. The powdery white vulcanization promoter compositionaccording to claim 2, wherein the inorganic filler (B) is at least oneselected from silica, calcium silicate, magnesium carbonate, andaluminum hydroxide.
 9. A rubber composition, wherein the powdery whitevulcanization promoter composition according to claim 2, andprecipitated silica are blended into a rubber.
 10. The rubbercomposition according to claim 9, wherein the powdery whitevulcanization promoter composition is contained so as to set the amountof the vulcanization promoter (C) into the range of 1 to 40 parts byweight based on 100 parts by weight of the precipitated silica.
 11. Thepowdery white vulcanization promoter composition according to claim 3,wherein the inorganic filler (B) is at least one selected from silica,calcium silicate, magnesium carbonate, and aluminum hydroxide.
 12. Arubber composition, wherein the powdery white vulcanization promotercomposition according to claim 3, and precipitated silica are blendedinto a rubber.
 13. The rubber composition according to claim 12, whereinthe powdery white vulcanization promoter composition is contained so asto set the amount of the vulcanization promoter (C) into the range of 1to 40 parts by weight based on 100 parts by weight of the precipitatedsilica.
 14. A rubber composition, wherein the powdery whitevulcanization promoter composition according to claim 4, andprecipitated silica are blended into a rubber.
 15. The rubbercomposition according to claim 14, wherein the powdery whitevulcanization promoter composition is contained so as to set the amountof the vulcanization promoter (C) into the range of 1 to 40 parts byweight based on 100 parts by weight of the precipitated silica.